EP3311428B1 - Verfahren zur herstellung eines stapels mit einer ersten elektrode/ einer aktiven schicht/ einer zweiten elektrode - Google Patents

Verfahren zur herstellung eines stapels mit einer ersten elektrode/ einer aktiven schicht/ einer zweiten elektrode Download PDF

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Publication number
EP3311428B1
EP3311428B1 EP16731102.6A EP16731102A EP3311428B1 EP 3311428 B1 EP3311428 B1 EP 3311428B1 EP 16731102 A EP16731102 A EP 16731102A EP 3311428 B1 EP3311428 B1 EP 3311428B1
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Prior art keywords
layer
electrode
active layer
resin
deposited
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English (en)
French (fr)
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EP3311428A1 (de
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Jean-Marie Verilhac
Simon CHARLOT
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Isorg SA
Trixell SAS
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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Commissariat a lEnergie Atomique CEA
Isorg SA
Trixell SAS
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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Priority to EP19175695.6A priority Critical patent/EP3550625B1/de
Publication of EP3311428A1 publication Critical patent/EP3311428A1/de
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/81—Electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/81—Electrodes
    • H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • H10K50/81—Anodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • H10K50/82—Cathodes
    • H10K50/828—Transparent cathodes, e.g. comprising thin metal layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/861—Repairing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
    • H01L2031/0344—Organic materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/301—Details of OLEDs
    • H10K2102/341—Short-circuit prevention
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the thickness of the active layer is generally of the order of 200-300 nm.
  • a filtration requires a solution having a good solubility which is not the case of all materials currently available for the active layers.
  • the filtration step is difficult to implement at the industrial level.
  • substrates with few defects are substrates with planarizing layers that are expensive.
  • This method therefore reduces the risk of short circuits.
  • the second conductive layer is very liquid. Indeed, it is then likely to infiltrate under the organic layer and come into contact with the first conductive layer beyond the engraved area under the defect.
  • the method requires that the first conductive layer is fully etched at the level of defects to avoid a short circuit.
  • the method requires that the first conductive layer is largely supergravated relative to the size of the opening in the active layer, because when the second conductive layer is deposited, it infiltrates a little under the active layer. and can thus generate a short circuit.
  • the method comprises an additional step (i) of removing the resin after the etching step (h).
  • the method comprises an additional step of depositing a passivation layer on the second conductive electrode, before the step (d) of depositing the resin layer.
  • a step (c) of local elimination by chemical etching of the first conductive layer, through the non-continuous zones of the active layer is provided after the step ( b).
  • the method may use any type of substrate that is not entirely opaque at the wavelength of this resin
  • this transmittance is at least 40%, or even at least 70%, at this wavelength.
  • This is, for example, a rigid glass substrate or FOP (Fiber On Plate in Anglosaxon terminology), or a flexible plastic substrate, for example of the PET type.
  • FOP Fiber On Plate in Anglosaxon terminology
  • flexible plastic substrate for example of the PET type.
  • a layer 2 of a conductive material On the substrate 1, was deposited during a step (a), a layer 2 of a conductive material. This layer 2 will form the first conductive electrode.
  • This electrode must be opaque to the wavelength of the resin used in the rest of the process.
  • this layer 2 is between 1 nm and several microns meters. Preferably, it will be strictly greater than 5 nm and less than 500 nm.
  • the material of layer 2 may be a metal, for example Au, Pd, Pt, Cr, Ti, Al or TiW.
  • the metal layer can be a massive layer.
  • a stack of at least two layers made of a metal and a metal oxide can for example be envisaged: Cr / ZnO, Au / TiO 2 , Au, MoO 3 or Cr / WO 3 .
  • it may be a stack of three layers, for example of the type: ITO / Ag / ITO, AZO / Ag / AZO or ZnO / Ag / ZnO.
  • the thicknesses of the stack are adjusted so as to modulate the optical spectrum of the stack and, in particular, to cut at the wavelength targeted for insolation of the resin.
  • optical simulations on Optilayer show that a tri-layer stack of AZO / Ag / AZO type with thicknesses of 300 nm / 10 nm / 300 nm would have a transmittance of 17% at 365 nm, while stacking with thicknesses of 600 nm / 10 nm / 600 nm would have a transmittance of 4% at 365 nm. It is therefore possible to modulate the thickness to ensure that the tri-layer cuts at the right wavelength. It is also conceivable to use more than three layers to make a Bragg mirror that cuts at the desired wavelength.
  • the organic material may be PEI, PEIE, a conjugated polyelectrolyte (poly [9,9-bis (3 '- (N, N-dimethylamino) propyl) -2,7-fluorene-alt-2,7- (9) , 9-dioctylfluorene)] (PFN)) or not (Nafion) or SAM (self assembled layer).
  • the layer 2 can be deposited by conventional vacuum techniques, for example by evaporation or sputtering. It can also be deposited by liquid, for example by a screen-printing technique, in atomic form or in the form of a dispersion of particles.
  • Other liquid deposition techniques are, for example, centrifugal coating, better known by its English name: "Spin-coating”, the flat-die coating better known by its English name of "slot-die”, heliography, flexography, inkjet, scraping deposit, spreading to the blade, better known as "doctor blade” or dip coating. In the remainder of the description, the English terms will be used again.
  • this first electrode 1 may act as anode or cathode.
  • the figure 1 shows that, on the layer 2, is deposited an active layer 3, in a step (b).
  • the thickness of this layer 3 is preferably between 10 nm and several micrometers.
  • the active layer consists of at least one material which is semiconductor in nature.
  • the donor semiconductor material may be a molecule, an oligomer or a conjugated organic polymer, that is to say with an alternation of single bonds and double bonds.
  • the mixture conventionally used is the regioregular poly (3-hexylthiophene) pair (P3HT RR) and the [6,6] -Phenyl C61 butyric acid methyl ester ([60] PCBM).
  • P3HT RR regioregular poly (3-hexylthiophene) pair
  • [6,6] -Phenyl C61 butyric acid methyl ester [60] PCBM.
  • Other donor polymers with a high gap PFB, TFB, PTAA, PCDTBT, etc.
  • PDPP3T, PCPDTBT, Si-PCPDTBT, PDDTT, etc. can advantageously be used.
  • acceptor material other materials may advantageously be used, of the C60, C70 or C80 derivative type (PCBM, indene-C60, indene-C60 bis adduct), acene diimide-type molecules, or polymer (F8BT , N2200) or any other inorganic compound.
  • PCBM C60, C70 or C80 derivative type
  • indene-C60 indene-C60 bis adduct
  • acene diimide-type molecules or polymer (F8BT , N2200) or any other inorganic compound.
  • the active layer may be a heterojunction of an electron donor material and an electron acceptor material in the form of a layer or a stack of several layers. It may also be a mixture at the nanoscale of the two materials in the form of volume heterojunction, that is to say, an intimate mixture of the two materials at the nanoscale.
  • the layer 3 may be deposited in a continuous layer or spatially located.
  • the active layer can be deposited by evaporation or co-evaporation, (case of molecules of low molar masses) or by liquid means (materials in the form of molecules, oligomers and polymers).
  • liquid coating techniques are of the spin-coating, slot-die, heliography, flexography, screen printing, inkjet, doctor blade or dip-coating type.
  • the active layer may be crosslinked so as to render it insoluble in the solvents present in the various layers deposited and / or used during the various etching steps provided for in the process.
  • P3HT and PCBSD can be mixed in a weight ratio of 1: 1 and deposited at a thickness of 200 nm. The layer is then annealed at 160 ° C. for 30 minutes in order to become insoluble in the usual solvents.
  • this active layer 3 must have a transmittance greater than 5% at the wavelength of the resin that will be used in the following process.
  • this transmittance is at least 20%, or even at least 50%, at this wavelength.
  • the active layer 3 comprises non-continuous zones, or defects, referenced 30 on the figure 1 .
  • defects may consist of micrometric holes or areas with large free volumes. It may be porosity or volumes that are not occupied by the polymer chains. They have dimensions of between 1 nm and several hundredenes of microns.
  • the figure 2 illustrates another step (c) of the method in which the conductive layer 2 is removed locally through the defects 30.
  • this step (c) may, in practice, be omitted.
  • etching preferably wet, that is to say by placing in contact with an etching solution.
  • the etching can be carried out by exposing the sample to vapors of the etching solution. In some cases, this elimination is obtained with a solvent.
  • etching solution that will generally be used in the following description.
  • the etching solution must be chosen so as not to degrade the electrical, optical and mechanical properties of the active layer.
  • the electrical properties of the active layer may be degraded due to an increase or decrease in its conductivity, or the generation of intrinsic or extrinsic electrical traps to the active layer.
  • the degradation of the optical properties of the active layer can for example result in a decrease in the absorption properties of light at the desired wavelength.
  • the degradation of the mechanical properties can be reflected in particular by detachment, cracking or loss of flexibility of the active layer.
  • the etching solution used will be selective, that is to say, it will be able to etch the conductive layer 2, without etching or attacking the active layer 3.
  • the etching solution will be an acid or a base. It can be pure or diluted in water or in a solvent orthogonal to the active layer, that is to say a solvent not likely to attack or dissolve the active layer.
  • An orthogonal solvent may be of the methanol, ethanol, ethylene glycol, di-ethylene glycol or isopropanol type.
  • the etching solution will be diluted in water and, preferably, in deionized water to avoid possible contamination with ions, especially metal ions (Na +, etc.).
  • the etching rate is between 1 and 1,000 / S.
  • the etching solution is provided on the active layer 3 and penetrates through the non-continuous zones 30 of this active layer.
  • the etching solution can be provided over the entire surface of the active layer or in a localized manner.
  • a localized deposit can be implemented in the case where several different devices are on the same matrix, some of them being sensitive to the etching solution.
  • the etching solution then reaches the conductive layer 2 through the zones 30, which makes it possible to locally eliminate the layer 2, in the zones identified on the figure 2 .
  • the latter may be etched in one or more steps and with one or more different etching solutions.
  • Etching is usually done concentrically from the defect in the active layer.
  • the duration of the etching will be chosen so that the surface of the etched zone or opening in the layer 2, to through a defect 30 of the active layer 3, at least equal to the surface of this defect.
  • the surfaces are here measured in the plane of layers 2 and 3.
  • FIG 29 which shows, seen from above, the layer 3, at a defect 30.
  • This is a micrometric hole whose input is schematically represented by a disk. The latter has a diameter d 1 .
  • FIG. 29 shows, bounded by a dotted line, the zone 20 of the layer 2 which has been etched and which is therefore devoid of conductive material.
  • This zone 20 is schematically represented in the form of a disk of diameter d 2 which is greater than d 1 .
  • d 2 is at least equal to d 1 and it will preferably be at least 2 d 1 or even 5 d 1 .
  • non-continuous area 30 may have a shape different from that of a disc. It can especially be an elongated crack.
  • the zone 20 has at least the dimensions of the defect and preferably a dimension at least 2 times or 5 times larger.
  • etching solutions may also be used successively, so as to completely burn the entire layer 2.
  • the stack illustrated at figure 2 will be rinsed, so as to stop the etching reaction and eliminate any residual traces of etching solution in the active layer 3.
  • This rinsing step will be carried out by dipping in at least one deionized water bath, an orthogonal solvent or an orthogonal water / solvent mixture.
  • the rinsing solution may be slightly acidic (if the prior etching is basic) and vice versa in order to buffer the pH of the solution during rinsing.
  • the rinsing of the stack can also be achieved by spraying a suitable liquid, alternatively a dipping in a bath.
  • an electrode 2 made of conductive oxides of ZnO type doped aluminum (AZO) or multi-layer type (AZO / Ag / AZO ...) can be advantageously used because of its ease to be etched ( a thickness of 125 nm can be etched in less than 30 s in an etching solution at 50 ° C) in dilute aqueous solutions of HCl or HCl / FeCl 3 (in particular sold under the name: TE100 from the manufacturer Transene).
  • the figure 3 illustrates another step (d) of this first mode of implementation of the method, in which a layer 4 of a negative resin is deposited on the active layer 3.
  • a negative resin is a resin that remains in place in the exposed areas
  • a positive resin is a resin that leaves in the insolated areas.
  • the thickness of this layer 4 is between 10 nm and 100 ⁇ m and preferably between 0.2 ⁇ m and 5 ⁇ m.
  • this layer 4 must be sufficient to cover the topology of the defects on the active layer.
  • This resin may be a fluororesin, for example a resin marketed under the name OSCoR4000 Orthogonal manufacturer. This resin may be a non-fluorinated resin of the SU8 range.
  • the resin may be deposited on the active layer 3 by evaporation or, preferably, by a liquid route. Preferably, this resin will be deposited by slot-die, spin-coating or spray-coating.
  • the figure 4 illustrates another step (e) during which the resin is insolated through the rear face 10 of the substrate. Consequently, it will be insolated in the zones corresponding to those where the electrode 2 is not present and in particular in the zones 20 in which the electrode 2 has been etched, as explained with respect to the figure 2 .
  • the ranges of insolation doses are those recommended in the resin data sheets and are typically of the order of 50-100 mJ.
  • the dose for crosslinking the resin will be adjusted according to the transmittance of the underlying layers (substrate 1, electrode 2, active layer 3) to the insolation wavelength of the resin.
  • the insolation will take place in an inert atmosphere, with a limited rate of oxygen, in order to limit the photooxidation of the active layer.
  • the figure 5 illustrates a next step (f) of the process in which the areas of the resin layer 4 that have not been insolated are developed.
  • This development is carried out thanks to a developer that must be orthogonal to the underlying layers and, in particular, to the active layer 3. In other words, the components of this developer do not dissolve or very little underlying layers .
  • the developer may be a product marketed by MicroChem under the name SU-8 Developer which is based on PGMEA.
  • the developer may be a product marketed under the name Orthogonal Developer 103 Solution by Orthogonal.
  • the figure 5 shows that after this step (f) of development, are obtained blocks 40 of negative resin which are located above the etched areas of the layer 2 and therefore, above the defects 30 present in the active layer 3. These studs 40 of negative resin make it possible to electrically pass the non-continuous or defect zones 30, that is to say to electrically isolate these zones 30 that can create electric leakage currents in the stack.
  • the figure 6 illustrates step (g) in which is deposited a layer 5 of a conductive material which will form the second conductive electrode.
  • This second electrode 5 may serve as anode or cathode.
  • This layer 5 is between 5 nm and 500 ⁇ m, preferably between 8 nm and 30 ⁇ m.
  • this layer 5 will be semi-transparent. It can also be opaque.
  • the stack when the stack is intended to form a photodiode, the latter can absorb the photons through this electrode.
  • semi-transparent electrode is used here to mean an electrode which has a transmittance greater than 10% at the desired wavelength of absorption of the photodiode. This transmittance is preferably greater than 40% or even 70% at this wavelength.
  • This electrode 5 may be formed by an organic, inorganic material or a mixture of both.
  • this layer 5 may be in the form of a monolayer of one of these materials, a mixture based on several of these materials or a stack of layers of these different materials, alone or in mixture , with specific interface layers.
  • the electrode 5 may be a monolayer or a multilayer comprising at least one of the following layers: metals (for example Ca, Ba, Al, Al, Ag, Pd, Pt, Ti or TiW), with a thickness of less than 10 nm in the case where the electrode must be semi-transparent, metal oxides in the form of monolayers (for example ITO, GZO, AZO or ZnMgO) or trilayers (for example ITO / Ag / ITO, ZnO / Ag / ZnO or AZO / Ag / AZO), conducting polymers of the PANI, PEDOT / PSS or Plexcore OC1100, graphene carbon-like conductive materials or carbon nanotubes.
  • metals for example Ca, Ba, Al, Al, Ag, Pd, Pt, Ti or TiW
  • metal oxides in the form of monolayers for example ITO, GZO, AZO or ZnMgO
  • trilayers for example ITO / Ag / I
  • Interface layers may possibly be deposited before the electrode 5 in order, for example, to block its output work.
  • the electrodes 2 and 5 have different output work.
  • either the output work of the conductive layer used is used, or an interface layer is placed which modulates the output work of the electrode so as to block the same output work to the desired value for the electrode. device.
  • LiF, Ca, Ba may be mentioned, with thicknesses of less than 5 nm; PEI or PEIE, metal oxides (TiO x , ZnO x , MoO 3 , CsCO 3 , WO 3 ), conjugated polyelectrolytes (PFN) or Nafion.
  • PEI or PEIE metal oxides (TiO x , ZnO x , MoO 3 , CsCO 3 , WO 3 ), conjugated polyelectrolytes (PFN) or Nafion.
  • a passivation layer 6 is deposited on the active layer between steps (c) and (d) previously described with regard to Figures 2 and 3 .
  • this buffer layer or passivation 6 is deposited between the active layer 3 and the resin layer 4. This layer 6 serves to protect the active layer 3 of the resin. This layer 6 is of electrically insulating nature.
  • It can be deposited by liquid or by evaporation.
  • It has a thickness of between 1 nm and 20 ⁇ m.
  • Parylene ® an oxide layer made by ALD (Al 2 O 3 type metal oxide, SiN type metal nitride) or a fluorinated polymer of the type sold under the name Cytop® by ASAHI.
  • FIGS 9 and 10 illustrate the steps (e) and (f) of insolation and development of the resin which are identical to those described with respect to Figures 4 and 5 .
  • This layer 6 is then etched by liquid or plasma, after the steps (e) and (f) of insolation and development of the resin.
  • This engraving step is illustrated by the figure 11 .
  • the layer 6 thus present under the studs 40 of resin which overhang the defect areas 30.
  • the figure 12 illustrates the step (g) of forming the second conductive electrode which is identical to that described with respect to the figure 6 .
  • the first electrode 2 is made of aluminum and has a thickness of 100 nm.
  • the electrode 2 is then etched using an RIE plasma treatment.
  • An active layer 3 of the heterojunction type volume of a thickness of 150 nm is deposited on the entire surface of the electrode 2 by spin-coating, or by other printing techniques of the slot die type, screen printing, gravure printing, jet ink or spray.
  • the active layer is a donor / acceptor mixture
  • the donor may be a regioregular poly (3-hexylthiophene) conjugate polymer and the acceptor a type molecule derived from 60PCBM fullerene.
  • the donor and the acceptor have a ratio of 1: 1 in the mixture.
  • the layer 3 is then rinsed thoroughly with deionized water and then dried.
  • a resin 4 of the type marketed under the name OSCoR4000 by Orthogonal is deposited by spin-coating on the active layer 3 to obtain a thickness of 1 micron.
  • the resin layer 4 obtained is annealed at 90 ° C for 1 min. It is then insolated by the rear face 10 of the substrate, with a wavelength of 365 nm and a dose of 100 mJ / cm 2 .
  • a so-called post-back step of 1 min at 90 ° C is performed It allows to finish hardening the resin in the insolated areas so that it does not leave during the development stage.
  • the resin layer 4 is then developed in the non-insolated zones for 90 s and with the aid of the developer marketed under the name "Developer 103" supplied by Orthogonal.
  • the second electrode 5 (anode) is deposited. It comprises a 100 nm interface layer of PEDOT-PSS on which is deposited an evaporated Ag layer whose thickness is 8 nm.
  • the substrate 1 is a flexible PET substrate.
  • the first electrode 2 (the cathode) is composed of two layers: a first opaque Cr layer with a thickness of 100 nm, and a second layer, called the interface layer, made of ZnO with a thickness of 30 nm.
  • the active layer has the same characteristics as in the previous example, the acceptor possibly being a type molecule derived from fullerene PCBSD type.
  • the active layer is annealed at 160 ° C for 30 min to crosslink and make it insoluble.
  • the stack is dipped in an etching solution of Cr.
  • This active layer is then rinsed thoroughly with deionized water and dried.
  • a resin of SU-8 type is deposited by spin-coating on the active layer to obtain a thickness of 2 microns. This layer is then annealed at 100 ° C. for 1 min.
  • the resin is then insolated by the rear face of the substrate, with a wavelength of 365 nm and a dose of 100 mJ / cm 2 .
  • the resin is then developed in the non-insolated zones for 90 s and using a PGMEA-based developer.
  • the electrode 5 (anode) is deposited. It comprises a 100 nm interface layer in PEDOT-PSS, on which is deposited a semi-transparent layer of Ag nanowire in the form of a percolating network in 2D.
  • the first electrode (cathode) 2 is made of a stack of three layers AZO / Ag / AZO, these three layers having respectively a thickness of 600 nm, 10 nm and 600 nm.
  • This first electrode 2 is deposited by cathodic sputtering and then localized with the standard techniques of microelectronics.
  • the active layer 3 has the same characteristics as those of the first example described above.
  • an AZO etching solution for example the solution sold under the name TE100 by the company Transene
  • an Ag etching solution for example, a solution of the 4CH type
  • the layer 3 is then rinsed thoroughly with deionized water and then dried.
  • a buffer or passivation layer made of Cytop® is deposited on the active layer 3 by spin-coating to obtain a thickness of 300 nm.
  • the surface of the layer 3 is activated by plasma to make it wetting.
  • a resin SU8 type is deposited on the layer to obtain a thickness of 1 micron.
  • the resin is then insolated by the rear face of the substrate, with a wavelength of 365 nm and a dose of 100 mJ / cm 2 .
  • the resin is finally developed using a PGMEA-based developer in non-insolated areas for 40 s.
  • the buffer layer 6 is etched by soaking for 30 seconds in a fluorinated solvent (for example sold under the name CT-SOLV 180) and using the resin pads as a mask.
  • a fluorinated solvent for example sold under the name CT-SOLV 180
  • the second electrode 5 is made as described in the first example.
  • step (c) in which the first electrode is locally removed, by etching through the non-continuous zones of the zone may be omitted. active.
  • the resin is insolated through the electrode 2 and in the zones corresponding to those of the defects 30 in the active layer 3.
  • the first electrode (layer 2) is therefore opaque.
  • the figure 13 illustrates a step (g) of this second embodiment of the method according to the invention, in which the second electrode 5 is made directly on the active layer 3, after the steps (a) to (c) illustrated in FIGS. Figures 1 and 2 .
  • This second electrode 5 may have the same characteristics as that described with reference to FIG. figure 6 , specifying that it must be at least transparent to the wavelength of the resin. It can also be filed using the same techniques.
  • This layer 7 may be deposited by evaporation or, preferably, by the liquid route, and in particular by slot-die, spin-coating or spray coating.
  • the thickness of this layer 7 is between 10 nm and 10 ⁇ m and preferably between 0.2 ⁇ m and 5 ⁇ m.
  • This resin may be a resin sold under the names Shipley S1818, Shipley S1814, Shipley S1828, Shipley Megaposit SPR220, AZ9260 series or AZTX1311-DUV by the company Microchemicals.
  • the figure 16 illustrates step (f) of the method in which the resin layer 7 is developed.
  • This step is carried out using a developer that is orthogonal to the underlying layers and in particular to the active layer 3 and the second electrode 5.
  • This etching is performed in the holes 70 formed in the resin layer 7.
  • This etching step is carried out chemically and / or physically.
  • an active layer 3 of heterojunction volume type about 150 nm thick is deposited on the entire surface of the electrode 2 by spin-coating, or by other printing techniques of the slot die type, screen printing, gravure, inkjet or spray.
  • a layer of resin sold under the name S1818 by the Shipley Company is deposited on the second electrode 5 at the turntable.
  • This layer has a thickness of 1 micron.
  • the figure 30 is a sectional view that represents such a matrix of pixels.
  • the figure 31 illustrates this conductive layer 8 and shows that this layer is localized, insofar as it consists of conductive lines electrically connecting the pads of the second electrode 5.
  • This second electrode 5 will not be described in more detail.
  • It may be made of a dielectric material deposited by evaporation (for example Parylene®), by PECVD, CVD, ALD, or deposited in solution (polystyrene, polyvinylphenol or Cytop® or cyclooelfin ).
  • This passivation layer is then etched chemically or physically between steps (k) and (g) illustrated in FIGS. Figures 23 and 24 .
  • An active layer 3 of the heterojunction volume type with a thickness of 150 nm is deposited on the entire surface of the first electrode 2 by spin-coating or other printing techniques such as slot die, screen printing, gravure printing, jet dye ink or spray.
  • the active layer is a donor / acceptor mixture
  • the donor may be a PBDTTT-C conjugated polymer and the acceptor a C60 fullerene molecule.
  • the donor and the acceptor have a ratio of 1: 2 in the mixture.
  • a passivation layer of Al 2 O 3 having a thickness of 50 nm is deposited by ALD.
  • the passivation layer is opened in places on surfaces with a diameter of less than 50 ⁇ m, in areas outside the electrode 2, and using ablation using an excimer laser. These open areas will allow the solvent to dissolve the resin, infiltrate through the buffer layer and perform the lift off step.
  • the resin is then stripped in an acetone bath for 1 min.
  • the electrode 5 (the cathode) composed of PEDOT / PSS and having a thickness of 50 nm is finally deposited by spin-coating.
  • This etching is performed in the holes 70 formed in the resin layer 7.
  • liquid means for example by dissolving in solvents, or physically, by using RIE type plasmas in particular.
  • the figure 26 illustrates step (j) in which a passivation layer 9 is deposited on the stack.
  • This layer 9 may have the same characteristics as the passivation layer described with reference to the figure 22 . It can also be filed using the same techniques. It will not be described in more detail.
  • the figure 27 illustrates the step (k) of removing the resin present in the layer 7.
  • the transmittance of the second electrode 5 does not matter.
  • An active layer 3 of heterojunction type volume of a thickness of 10 nm is deposited on the entire surface of the electrode 2 by spin-coating or other printing techniques slot die types, screen printing, gravure printing, inkjet or spray.
  • the active layer is a donor / acceptor mixture
  • the donor may be a TFB-type conjugated polymer and the acceptor a PCBSD-type fullerene type molecule.
  • the donor and the acceptor have a ratio of 1: 2 in the mixture.
  • the active layer is annealed at 160 ° C for 30 min to crosslink and become insoluble.
  • the layer 3 is then rinsed thoroughly with deionized water and then dried.
  • a resin layer of the type sold under the name S1818 by Shipley is deposited on the active layer, then insolated by the rear face of the substrate with a wavelength of 365 nm and a dose of 80 mJ / cm 2 .
  • the resin layer is developed using the developer marketed under the name MF319 for 40 s.
  • the active layer is then etched using an Argon RIE plasma.
  • a 50 nm passivation layer of Al 2 O 3 having a thickness of 50 nm is then deposited by ALD.
  • the passivation layer is opened in places on surfaces with a diameter of less than 50 ⁇ m, in areas outside the electrode 1, and using ablation using an excimer laser. These open areas will allow the dissolving solvent of the resin to infiltrate through the buffer layer and perform the lift off step.
  • the resin is then stripped in an acetone bath for 1 min.
  • the electrode 5 (the cathode) composed of a layer of Al with a thickness of 3 nm and a layer of Ag with a thickness of 7 nm is finally deposited by evaporation under vacuum.
  • the resin layer may be deposited on the entire surface of the stack or only in localized areas. This localized deposit can be made using a mask.
  • this method makes it possible to solve the problem of parasitic electrical leakage currents through an organic semiconductor layer of a stack, by electrically passivating the fragile zones of this organic layer, whether holes or zones of different morphologies.
  • the method can provide, as in the document FR-2,991,505 to locally etch an electrode zone under the active layer, through the defects of this layer.
  • This local etching step (c) makes the process even more efficient for passing the defects of the active layer.
  • this method provides for the deposition of a positive or negative resin which is insolated through the electrode present under the active layer.
  • the method makes it possible to open a positive resin or to deposit a negative resin, precisely above the fragile zones, at the origin of the electric leakage currents.
  • the opening or the deposition of the resin is thus self-indexed on the defects present on the active layer.
  • the resin allows, thanks to specific steps, to electrically isolate faults that can create electric leakage currents in the stack by repairing them locally.
  • the first mode of implementation is a preferred mode. Indeed, it is this process that has the least steps and is the easiest to implement. In particular, it does not include a step of etching the second electrode 5 or the active layer 3 which are, in addition, difficult steps to achieve. Finally, this method is best suited to obtaining pixel matrices.
  • the method according to the invention may advantageously be used to increase the performance and decrease the defects of organic electronic devices used in discrete components or in more complex systems of the passive or active matrix type. These devices may be organic or hybrid organic / inorganic type.

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Claims (4)

  1. Verfahren zur Herstellung eines Stapels vom Typ erste Elektrode/aktive Schicht/zweite Elektrode, welcher für eine elektronische Vorrichtung bestimmt ist, insbesondere vom Typ organischer Lichtdetektor oder organische Solarzelle, welches folgende Schritte beinhaltet:
    (a) Ablagern einer ersten Schicht (2) leitfähigen Materials auf der Vorderseite eines Substrates zum Bilden der ersten Elektrode,
    (b) Ablagern einer aktiven Schicht (3), in Form einer dünnen organischen Halbleiterschicht, wobei diese Schicht nicht durchgängige Bereiche beinhaltet,
    (d) Ablagern einer Harzschicht (7) auf der dem Substrat, welches mindestens teilweise transparent ist, abgewandten Seite des Stapels,
    (e) Besonnen der Harzschicht (7) über die rückwärtige Seite (10) des Substrates, wobei die erste Elektrode (2) auf der Wellenlänge, eingesetzt zum Besonnen der Harzschicht (7), undurchsichtig ist, wobei das Harz (7) besonnt wird in Bereichen, die den Bereichen, wo die erste Elektrode (2) nicht anwesend ist, entsprechen.
    (f) Entwickeln der Harzschicht,
    (g) Ablagern einer zweiten Schicht (5) leitfähigen Materials zum Bilden der zweiten leitfähigen Elektrode,
    dadurch gekennzeichnet, dass:
    das Harz (7) positiv ist, wobei der Schritt (f) zum Bilden von Löchern (70) in der Harzschicht (7) im Bereich der nicht durchgängigen Bereiche (30) führt, und der Schritt (g) zwischen den Schritten (b) und (d) erfolgt, wobei ein Schritt (h) des Gravierens der zweiten leitfähigen Elektrode (5) nach dem Schritt (f) erfolgt.
  2. Verfahren nach Anspruch 1, welches einen zusätzlichen Schritt (i) beinhaltet, bestehend im Entfernen des Harzes (7) nach dem Schritt (h) des Gravierens.
  3. Verfahren nach Anspruch 1 oder 2, welches einen zusätzlichen Schritt beinhaltet, bestehend im Ablagern einer Passivierungsschicht auf der zweiten leitfähigen Elektrode vor dem Schritt (d) des Ablagerns der Harzschicht (7).
  4. Verfahren nach einem der Ansprüche 1 bis 3, bei welchem ein Schritt (c) des lokalen Eliminierens durch chemischen Angriff der ersten leitfähigen Schicht durch die nicht durchgängigen Bereiche (30) der aktiven Schicht nach dem Schritt (b) erfolgt.
EP16731102.6A 2015-06-16 2016-06-16 Verfahren zur herstellung eines stapels mit einer ersten elektrode/ einer aktiven schicht/ einer zweiten elektrode Active EP3311428B1 (de)

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FR1555480A FR3037723B1 (fr) 2015-06-16 2015-06-16 Procede de realisation d'un empilement du type premiere electrode / couche active / deuxieme electrode.
PCT/EP2016/063922 WO2016202938A1 (fr) 2015-06-16 2016-06-16 Procédé de réalisation d'un empilement du type première électrode / couche active / deuxième électrode

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CN109103215B (zh) * 2017-06-21 2021-03-09 京东方科技集团股份有限公司 一种有机发光二极管显示面板及其制作方法、显示装置
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KR20180019165A (ko) 2018-02-23
KR102629662B1 (ko) 2024-01-25
CN107925005B (zh) 2022-04-08
US20180159060A1 (en) 2018-06-07
EP3550625A1 (de) 2019-10-09
JP2018521507A (ja) 2018-08-02
EP3550625B1 (de) 2021-07-21
CN107925005A (zh) 2018-04-17
JP6830453B2 (ja) 2021-02-17
WO2016202938A1 (fr) 2016-12-22
US10559771B2 (en) 2020-02-11
EP3311428A1 (de) 2018-04-25
FR3037723A1 (fr) 2016-12-23
FR3037723B1 (fr) 2019-07-12

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